The photophysics of copper(II) porphyrins has been studied by a variety of techniques. Our own transient resonance Raman data on Cu(II) tetraphenylporphyrin (CuTPP) provided the first direct experimental evidence for the involvement of excited states other than triplets in the relaxation dynamics of the first excited singlet state. However, it is not yet clear if these excited states are charge-transfer (CT) or d-d in character. In order to provide definitive assignments for the relaxing states, we have undertaken investigations of a variety of substituted CuTPP's, where the phenyl moieties contain para substituents. We will begin the study by obtaining luminescence and time-resolved electronic absorption (TREA) spectra of these CuTPP's in order to determine the extent to which the substituents modulate the energies of triplet states. The TREA work will be conducted at the RLBL. Then, we will probe the relaxing states directly by time-resolved resonance Raman (TRRR) spectroscopy at Haverford. We expect that CT and d-d states will be modulated differently by inductive and resonance effects by the substituents. For example, the extent of CT determined by TRRR, will be very sensitive to the reduction potential of the porphyrin macrocycle, which is modulated by para-phenyl substitution.